Water-insoluble monoazo-dyestuffs



United States Patent 0. "Ice 6 Claims. 61. 260-203) The presentinvention relates to new water-insoluble monoazo-dyestutfs and to aprocess for preparing them; more particularly it relates to dyestuffs ofthe general formula wherein X represents hydrogen, a halogen atom, analkyl, alkoxy, aryloxy, alkylsulfone, aiylsulfone, cyano or carboxylicacid ester group, R represents hydrogen, a halogen atom or an alkoxygroup, Y stands for a 80 or CO- group, Ar represents a phenylene ornaphthylene radical which may be substituted by halogen atoms, alkyl oralkoxy groups, Z represents a carboxylic acid amide or sul fonic acidamide group which may contain substituents, an acylamino,alkylsulfonylamino or arylsulfonylamino group, n stands for 1 or 2, andA represents the radical of a coupling componentfree from sulfonic acidand carboxylic acid groups and capable of coupling in a positionadjacent to a hydroxyl group.

I have found that valuable, water-insoluble monoazodyestuffs areobtained by coupling a diazonium compound of an amine of the generalformula wherein X represents hydrogen, a halogen atom, an alkyl, alkoxy,aryloxy, alkylsulfone, arylsultone, cyano or carboxylic acid estergroup, R represents hydrogen, a halogen atom or an alkoxy group, Ystands for a SO or CO-group, Ar represents a phenylene or naphthyleneradical which may be substituted by halogen atoms, alkyl or alkoxygroups, Z represents a carboxylic acid amide or sulfonic acid amidegroup which may contain substituents, an acylamino, alkylsulfonylaminoor arylsulfonylamino group, and n stands for 1 or 2, with a couplingcomponent free from sulfonic acid and carboxylic acid groups and capableof coupling in a position adjacent to a hydroxyl group.

The amines used as diazo components in the process of the presentinvention can generally be prepared by condensing a nitrobenzoic acidchloride or nitrobenzene sulfonic acid chloride of the formula with anaromatic amine of the general formula wherein X, R, Ar, Z and n have themeanings indicated above, and subsequent reduction. They can, however,

also be prepared by other methods, for example by condensing anacetylaminobenzene sulfochloride of the formula NH.CO.OH

with the above-mentioned aromatic amines of the formulafl N- Ar -(Z) andsubsequent splitting oiT of the acetyl group. As appropriate aromaticamines of the formula H NAr--(Z) which are suitable for the preparationof the diazo components, there may be mentioned for example:aminobenzene carboxylic acid amides, aminobenzene dicarboxylic aciddiamides, aminobenzene sulfonic acid amides and aminobenzene disulfonicacid diamides, the amide groups of which may contain substituents,furthermore monoacylated phenylene diamines, diacylated phenylenetriamines and aminobenzenes containing one or two alkylsulfonylamino orarylsulfonylamino groups, whereby these amines may contain in thearomatic radical further substituents, such as halogen atoms, alkyl oralkoxy groups.

The diazonium compounds may be prepared in known manner. In some casesthe diazonium compounds are difiicultly soluble in an aqueous medium andare separated in the form of their salts. These salts can be isolatedand coupled in the form of a moist paste. In these cases it isadvantageous to carry out the diazotization in a suitable organicsolvent, such as glacial acetic acid, acetone, dioxane,tetrahydroiurane, formamide, dimethyl formamide or dimethyl sulfoxide,and to combine the solution of the diazonium compound so obtained withthe coupling component.

As coupling components there are used in the process of the presentinvention compounds capable of coupling in a position adjacent to ahydroxyl group, for example aromatic or heterocyclic hydroxyl compoundsand compounds containing in an open carbon chain or in a heterocyclicring an enolizable or enolized ketomethylene group.

Compounds of this kind are, in particular, the arylamides for example,derivatives of 5-pyrazolone, such as 1-aryl- 3-methyl-S-pyrazolones,1-aryl-5-pyraz0lone-3-carboxylic acid esters or1-aryl-5-pyrazolone-3-carboxylic acid amides, whereby the aryl radicalmay contain the abovementioned non-solubilizing substituents,furthermore 2,4- dihydroxy-quinoline or barbituric acid derivatives.

The novel dyestuffs can be prepared by known methods, for example bycoupling the diazonium compounds with the coupling components in anaqueous medium, advantageously in the presence of a dispersing agent orin the presence of an organic solvent. In order to obtain a favorablegranular condition of the azodyestuffs, it is advantageous in some casesto add resin soap to the reaction mixture after coupling and/or to heatthe mixture, for example for some time at the boil, or to mix, whilestirring, and/ or heating, if desired, the isolated dyestuff in a moistor dry state for some time with an organic solvent, such as pyridine,glacial acetic acid, dimethylformamide, quinoline or chlorobenzene.

The dyestuffs obtainable by the process of the present invention arewater-insoluble pigments which are distinguished especially by a goodfastness to solvents. They are suitable for the preparation of coloredlacquers, lake formers, solutions and products prepared from acetylcellulose, natural resins or synthetic resins, such as polymerization orcondensation resins, for example aminoaaoonoo plasts or phenoplasts, aswell as solutions and products 7 prepared from polystyrene, polyolefins,such as polyethylene or polypropylene, polyacryl compounds, polyvinylcompounds, for example polyvinyl chloride or polyvinyl acetate,polyesters, rubber, casein or silicon resins.

Furthermore, the novel dyestutls can be used for pigment printing on asubstratum, especially on a textile fiber and also on other flatstructures, for example on paper. They can also be used for otherpurposes, for example in a finely divided form for dyeing rayon ofviscose or cellulose ethers or cellulose esters, polyamides orpolyurethanes in the spinning solution or for coloring paper.

The following examples illustrate the invention, but they are notintended to limit it thereto, the parts being by weight unless otherwisestated, and the relationship of parts by weight to parts by volume beingthe same as that of the kilogram to the liter.

Example 1 198 parts of 3-nitro-4-methoxy-benzoic acid were heated underreflux in 200 parts by volume of thionyl chloride until the evolution ofhydrogen chloride had ceased. The thionyl chloride in excess was thendistilled off in an air current, the residue was cooled and dissolved in500 parts by volume of acetone. The solution of3-nitro-4-methoxy-benzoic acid chloride so obtained was filtered andunder stirring and external cooling at a temperature of 15 to 20 C. runinto a solution of 140 parts of 4-aminobenzoic acid amide in 150 partsby volume of pyridine, 600 parts by volume of dioxane and 150 parts byvolume of water. When the condensation was complete, the reactionmixture was acidified with hydrochloric acid, the reaction product wasfiltered olT with suction and Washed. The 1-( 3-nitro-4-methoxybenzoylamino -benzene-4-carboxylic acid amide soobtained melted at 302 to 304 C. It was converted by catalytic reductionwith hydrogen in the presence of Raney-nickel in methanol into the 1- (3-amino-4'-methoxybenzoylamino) -benzene-4-carboxylic acid amide of theformula 2 112N.0 o-Q-ma-o o- The product melted at 291 C.

Example 2 28.5 parts of 1-(3'-amino-4'-methoxybenzoylamino)-benzene-4-carboxylic acid amide were heated to 70 C. with 600 parts ofwater and 60 parts by volume of 5 N- hydrochloric acid. The solution soobtained was cooled to C., diazotized with parts by volume of a 5 N-solution of sodium nitrite and the diazo solution obtained wasclarified. In the meantime 37 parts of 1-(2',3'- hydroxynaphthoylamino)2,5 dimethoxy-4-chlorobenzene were dissolved in hot dilute sodiumhydroxide sowas stirred for 1 hour and boiled for 1 hour.

lution. The .hotsolution was cooled, clarified and precipitated at 0 C.with acetic acid in the presence pf a reaction product from about 20mols of ethylene oxide and 1 mol of oleyl alcohol. The suspensionobtained was heated to 65 to 75 C. and coupled at this temperature withthe diazo solution mentioned above.v During the coupling operation themixture was neutralized .by the addition of a sodium acetate solution.The mixture was then stirred for 1 hour, boiled for 1 hour and thenfiltered off with suction, washed and dried. It was advantageous to addresin soap to the dyestutf after coupling. There was obtained a dyestuffof the formula.

OH (iJCHs It is a bluish-red pigment which, when incorporated inpolyvinyl chloride, a lacquer or a printing ink, yields Carmine redcolorations possessing good fastness properties, especially a very goodfastness to solvents.

Example 3 32.1 parts of 1-(3f-amino-4'-methoxybenzoylamino)-benzene-4-sulfonic acid amide were stirred for some time with 60 partsby volume of 5 N-hydrochloric acid, The paste formed was diluted withwater and diazotized at 15 C. with 20 parts by volume of a 5 N-solutionof sodium nitrite. The clarified diazo solution was run at 18 C. into anaqueous suspensionof 29 parts ofl-acetoacetylamino-2,5-dirnethoxy-4-chlorobenzene, which had beenprepared by dissolving this compound in dilute sodium hydroxide solutionand reprecipitating itwith glacial acetic acid in the presence of areaction product from about 20 mols of ethylene oxide and 1 mol ofoctadecyl alcohol. During the coupling operation the mixture wasneutralized by the addition of a sodium acetate solution. When thecoupling was complete, the mixture 7 The dyestuff was then filtered olfwith suction, washed and dried. It was advantageous to add resin soap tothe dyestuif after coupling. A yellow dyestufi of the formula OCH; wasobtained.

The yellow colorations produced with this dyestufl? show in variousworking media, such as lacquers, printing inks and plastics, a goodfastness to solvents.

Emample4 30.4 parts of 1-(3'-am-ino 4 chlorobenzoy-lamino)-4-acetyl-aminobenzene were stirred for some time with 400 parts by volumeof glacial acetic acid and 50 parts by volume of 5 N-hydrochloric acid,the hydrochloride of the amine being formed. 20 parts by volume of a 5N- solution of sodium nitrite wereadded, the solution was stirred for ashort time, then diluted with 300 to 40(1 parts by volume of water andthe solution so obtained was clarified. The diazo solution so obtainedwas coupled with a clarified solution of 30 parts of 1-(2',3'-hydroxynaphthoylamino) 4 methoxybenzene in 1000 with water. The moistdyestuff cake was stirred with 1000 parts by volume of chlorobenzene,the water was distilled off azeotropically and the mixture was heatedfor another hour under reflux. The dyestuif was then filtered parts byvolume of pyridine, the dyestuff being formed. 5 off with suction andthe adhering chlorobenzene was re- The mixture was stirred for about 1hour, then diluted moved by distillation with steam or by washing withwith water, and the dyestuff was filtered 01? with suction, methanol.After drying there was obtained a dyestuft of washed'and dried. Therewas obtained a dyestufl of the the formula formula. 00H,

10 CONH-@-NH.GO.CH;

' ll 01 0 ONH 0 0 .NHz

\ c i OH o Ha 1i CO-NHOCH3 0H in 00113 When incorporated in polyvinylchloride, at lacquer or a printing mk, 1t yields carimne red coloratlonsof good It is a red powder. The colorations of the various workfasmessto hght and to Solventsing media, such as lacquers, plastics andprinting inks, with Example 6 fllstdyesmfi are dlstmgulshed y goodfastness to $01- The coupling was carried out as described in Example vE a l 5 5 and, when the coupling was complete, the dyestuif x mp eformed was filtered OE With suction and dried. There 28.5 parts of1-(3-amino-4'-methoxybenzoylamino)- was obtained a pigment possessing ahard grain and exhibbenzene-4-carboxylic acid amide were diazotized asdeiting a low tinctorialstrength. By heating this pigment scribed inExample 2. Furthermore, 37 parts of 1-(2',3- to 95 C. in 1000 parts byvolume of dimethyl-formamide, hydroxynaphthoylamino) 2,4 dimethoxy 5chlorosubsequently filtering with suction, washing and drying a benzenewere dissolved in hot dilute sodium hydroxide pigment was obtained whichin its properties corresponds solution, the solution was cooled andclarified. Both to the dyestufi described in Example 5. solutions wererun simultaneously at room temperature Instead of dimethylformamideother organic solvents, within about 1 to 2 hours into a mixture of 400parts by for example quinoline, may be used.

volume of water and 22 parts by volume of glacial acetic acid in thepresence of a reaction product from about 20 mols of ethylene oxide and1 mol of oleylalcoh-ol. The mixture was stirred until the coupling wascomplete, the dyestufl formed was filtered off by suction and washed Thefollowing table indicates a number of further components which can beused in the process of the present invention, and also the tints of theprinting inks prepared with the monoazo-dyestufis obtainable from thesecomponents.

Diazo component Coupling component Tint1-(3-amin0-bcnz0y1amino)-benzene-4-sulionic acid amide1-(2,3-hydroxynaphthoylamino)-4-methoxybenzene Red. 1-(3anino-4-methylbenzoyl-amino)-benzene4-sulfonlc acidl-g,3-hydroxynaphthoylaml.n0)-2,5-dimeth0xy-4chloro- Do.

am e. enzene. 1-(3-ami.uo-4-methoxybenzoyl-amlno)Aacetylaminobenzene doCarmine. l-(3{gmin%-4-meth0xybenzoyl amiuo)-benzene-4-carboxylicl-acetoacetylamino-2,5-dimethoxy-4-chlor0benzene. Yellow.

ac aim e. 7 Do. I I 1-phenyl-3-methyl-5-pyraz0l0ne Rcddish-yellow. 1-(3'igmgiio -methoxybenzoyl-amino) benzene-leukemic 1-(2,3-hydroxynaphthoylamino) -2,ldimethoxy-E-chloroben- Ruby.

ac a e. zene.

D0- l-acet0acetylamino-2,4-dimethoxy-5-chlorobenzene Yellow. D02,4dihydroxy-qui.noline Reddish-yellow.1-(3'-amino-4-methoxybenzoylamino) -2-chlorobenzene-5- 1- (2' ,3-hydroxynaphthoylamin0) -2,4-dimethoxy-5-chloroben- Claret.

carboxylic acid amide. zene.1-(3-amino4-meth0xybenzoylamlno)-benzene-3,5-bis-carb0xylic1-(2,3-hydroxynaphth0ylamin0)-2,5'dimeth0xy-4-chl0ro- Carmine.

acid amide. benzene.

D0 1-(2,3'-hydroxynaphthoylamino)-2,4-dlmethoxy-5-chloroben- Claret.

zene. 1-(3'-amino-4'-methoirybenzoylaminc)-2-meth0xybcnzene-5- do Do.carboxylic acid amide.1-(3'-amino-4-methoxybenzene-sulfonylamino)-benzene-4- do.- Bluish-red.

carboxylic acid amide. 1-(3-amin0-4-hlombcnzeue-sulfonylamlno)-benzene-4-car-1-(2,3-hydroxynaphthoylamino)-4-methoxybenzene Red.

boxylic acid amide.

Do 1-acetoacety1amino-2, fi-dimethoxyl-chlorobenzene Yellow.1-(3'-amino-4-chlcrobenzoylamino)-4-acetylaminobenzene1-(2,3-hydroxynaphthoylamino)-2-methoxybenzene Red.

Do. 1-acet0acetylamino-2,5dimeth0xy-4-chl0robenzene Yellow. 1-(3anino-y-chlorobenzoylamlno)-benzene-4-sulfonic acidl-(2',3-hydr0xynaphth0ylamino)-4-rneth0xybenzene Red.

am e.

Do- 1-(2,3-hyd.roxynaphthoylamino)-4-ethoxybenzene Do. l-ligianino--chlorobenzoylamino)benzene-tearboxylic acid1-(2,3-hydroxynaphthoylamino)-4-methoxybenzene Do.

a. 1-(:ifimino-Mchlorobenzoylamino) -2-ch10robenzene-5-carb oxylic d0D0.

ac am e. I 1-(3'-amino-4-chlorobenzoylamino) -2-chlor0benzene-S-sulfonic-dc Do.

acid amide. 1-(3'-amlno-4-carbomethoxybenzoylamino)-benzene-4-cardol Do.

boxylic acid dimethylamide.1-(3-amino-4-methoxybenzoylamino)-benzene-4-carboxylic acid1-(2',3'-hydroxynaphthoylamino)-2,4-dimcthoxy-E-chloroben- Bluish-red.

methylamide. zene.

Do do Do. 1-(3'-am1no-4'-methoxybenzoylamino)-bcnzene-4-carb0xylic doDo.

acid-n-propylamide. 1-(3-amin0-4-methoxybenzoylamlno)-benzene-4-carboxylic do.- Do.

acid-n-butylamide.1-(3'-amin0-4'-meth0xybenz0ylamln0)-2-chlorobenzene-5-cardo Do.

boxyllc acid-methylamide.1-(3'-amiuo-4'-methoxybenz0ylamino)-2-methylbenzene-5-cardo Do.

boxylic acid amide.

Diazo component Coupling component Tint1-(3'-anino-4-methoxybenzoylamino)-benzcne-3-su1fonic acid do; Do.

aml e. 1-(3-amino-4-methoxybenzoylamino)-benzeue-4-suifonic acid .d0 Do.

methylamide. t 1-(3-amino-M-methoxybeuzoylamino)-benzcne-4-sulionic aciddo- Do.

cthylamide. 1-(3-arnino-4-methoxybenzoylamino)-benzene-3-carboxylic do.Do.

acid amide. 1- (3amino-4-methoxybenzoylamino)-2-chIorobenzene-5- do Do.

sulfonic acid amide. 1- (3'-an1ino-4-methoxybenzoy1amino)-2-methoxybenzcne-5- do Do.

sulfonlc acid amide.1-(3-amino-4-methoxybenzoylami.no)-2-chlorobcnzene-4-su1- do.. 7 Do.

ionic acid amide. 1-(3-an1ino-4-mcthoxybenzoylamino)-4-acetylammobenzenedo Do. 1- (3-amino4-methoxybenzoylamino) -4-propionylammobendo; 4'. D0.

zene. 1-(3-amino-4'-methoxybenzoylamino)-?rchloro-5acetylaminodo Do.

benzene. 1-(3-ag1ino-4'-ethoxybenzoyiamino)-benzene-4-carboxylic acid doI Do.

aml e. 1-(3-amino-benzoylamino)-benzene-4-sulfonic acid amide1-(2,3'-hydroxyuaphthoylamiuo)-4-acetylaminobenzene Red. 1-(3anino-4-methy1benzoyiamino)-benzene 4-su1fouic acid1-g;3-hydroxynaphthoylamino)-2,4-dlmeth0xy-5-chlor0- Do. aml e. Venzenc. 1- (3-amino-4-methy1benzoylamino) -benzene-4-car- 1-(2,3-l1ydroxynaphthoylamino) -2,5-di.methoxy-4-ehloro- D0.

boxylie acid amide. I benzene. V1-(3amino-4-methylbenzoylam1no)-2-ch1orobenzene-5-car-1-(2,3-hydroxynaphthoylamino) -2,4-d.imethoxy-5-chloro- Do.

boxylic acid amide. benzene. w a v i1-(3-amino-4-methoxybenzoyiamino)-benzene-4-carboxylic 1-(2,3hydroxynaphthoylamino)-2-methoxy-4-aeety1ammo-5- Carmine;

acid amide. chlorobenzene.

Do 1-(2,3-hydroxynaphthoy1amino)-2Fmethy1-5-chlorobenzene Do. Do1-(2,3-hydroxynaphthoylamino)-4-methoxybenzene, Re Do1-(2,3-hydroxynaphthoylamino-2-methyle iemethoxybenzene- Bluish-red. D01- (2,3 -hydroxynaphthoy1amino)-2,4-dimethoxyb enzene D 0. Do2-(2,3-hydroxynaphthoylamino)-3-methoxy-diphenylene oxiden Do. Do.2-(2,3-hydroxynaphthoylamino)-naphthalene- Do. Do1-(2',3-hydroxynaphthoylamino)naphthalene Do. Do.l-acetoacetylamino-2-methoxyl-accty1amino-5-chlorobenzene Yellow. Do1-p-tolyl-3-methyl-5-pyramlone Reddish-yellow. Do 1-(2,3-hydroxynapl1thoylamino)-3-nitrobenzene 1 Carmine. Do 71-(2,3-hydroxynaphthoylamino)-2-methoxybenzene-5-car-' Do.

- 7 'boxylic acid amide.1-(3'-3,I]1l11O-4'-methOXYbBQZOyIfimiIlO)-b011ZBI1e-4-Cal'b0xy1i01-(2,3-hydroxynaphthoylamino)-2,5-dimethoxy-4-eh1oroben- Red.

acid methylamide. zene. r I 1-(3-amino-4-meth0xybenzoylammo)-2-methylbenzene-5- do Do.

sulfonic acid amide. v1-(3-amino4-methoxybeuzeue-suliouylammo)-benzene-4- do- Do.

carboxylic acid amide. r V1-(3-am.ino-4-chlorobenzoylamino)-benzeue-4-carboxyhc acid1-(2,3-hydroxy-naphthoylamiuo)-4-ethoxybenzene Yellowish-red.

amide. V

Do 1-(2,3-hydroxynaphthoylamino) -4-acetylaminobenzcne Do. Do1-(2,3-hydroxynaphthoylamiuo) -2-methylbenzene Do. Do1-(2,3'-hydroxynaphthoylamiuo)-2-methyi-4-chlorobenzen Do. Do 1-(2,3-hydroxynaphthoylamino)-4-benzoylaminobenzeue Red. Dol-acetoacetylamino-Z,5-dimethoxy-4chiorobenzene Yellow.1-(3-amino-4-chlorobenzoylamino)-benzene-4-carboxylic acid1-(2,3-hydroxynaphthoylam1no)-4-methoxybenzene Yellowish-red.

meth lami e.

D0 1-(2,3-hydroxynaphthoylamino)-2-methoxybenzene -Do. 1-(3amino-4-ch1orobenzoylaruino)-benzene-4.-sulfonic acid1-(2,3-hydroxynaphthoylamino)-4-acety1aminobenzeue Do.

arm a. 1- (3-amino-4-chlorobenzoylamino) -2-chlorobcnzene-5-cardo D0.

boxylic acid amide. V1-(3-amin0-4-chlor0benzoyl-amino)-4-acety1aminobenzenc1-(2,3'-hydroxynaphthoylam no)-4-acetylaminobenzene Do.1-(3-ainlino-4gcarbgmcthoxybenzoylamino)-benzenc-4-car-1-(2,3-hydroxy'naphthoylammo)-4-ethoxybenzene Red. boxy 'c aci am e.I-(3-amiuo-4-carboethoxybenzoylamino)-benzeue 4-car-1-(2',3-hydroxynaphthoylami.uo)-4-methoxybenzene.' Do.

boxylic acid amide. r

I claim: I l of hydrogen, chlorine, methyl and methoxy, Z is bound 1. Awater-insoluble monoazo-dyestufi of the formula onto the benzene radicalin a position selected from the r 5 5 groupconsistingof meta-andpara-.tothe ..NH*.group f= -5 H and represents a member selected fromthe group con- X sisting of carboxylic acid amide, carboxylic acid mono-(ZM alkylamide,"sulfonic acid amide, sulfonic acid monoalkyl- N Y amideand-alkoylamino, n stands for one of the numbers 6O 1 and 2 andArepresents the radical offa coupling com- Wherein X represents amer'nberselected from the group consisting of hydrogen, chlorine, methyl,methoxy, ethoxy, carbomethoxy and carboethoxy, Y represents a memberselected from the group consisting of CO and S0 R represents a memberselected from the group consisting f ponent selected from'the groupconsisting of a 2,3-hydroxynaphthoic acid arylamide of theben'zene,fnaphthalene and diphenyl oxide series, an acetoacetic acidarylamide of the benzene series, '1 phenyl 3-inethyl 5-pyrazo- 5 loneand l-p-to1yl-3-methyl-5-pyrazolone. r

2. The monoazo-dyestuif of the formula New 3. The monoazo-dyestuff ofthe formula H0 30NH o1 N=N-- B C H:

0 0H, HzN-OC-QNH-O 4. The monoazo-dyestuff of the formula H0 0 ONH 0 CH:

mc-NH-ofl- NH0 c 5. The monoazo-dyestufi of the formula 6. Themonoazo-dyestuff of the formula References Cited by the Examiner UNITEDSTATES PATENTS 2,915,518 12/59 Fischer 260-203 FOREIGN PATENTS 889,7399/53 Germany.

CHARLES B. PARKER, Primary Examiner.

1. A WATER-INSOLUBLE MONOAZO-DYESTUFF OF THE FORMULA